Manufacturing a base stock from ethanol

ABSTRACT

Methods and a system for manufacturing a base stock from an ethanol stream are provided. An example method includes dehydrating an ethanol stream to form an impure ethylene stream, recovering an ethylene stream from the impure ethylene stream, and oligomerizing the ethylene stream to form a raw oligomer stream. A light olefinic stream is distilled from the raw oligomer stream and blended with the ethylene stream prior to the oligomerization. A heavy olefinic stream is distilled from the raw oligomer stream and hydro-processed to form a hydro-processed stream. The hydro-processed stream is distilled to form the base stock.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/721,246, filed on Aug. 22, 2018, the entire contents of which areincorporated herein by reference.

FIELD

The techniques described herein provide systems and methods formanufacturing a lubricant base stock from ethanol. The ethanol isdehydrated to generate an ethylene stream that is oligomerized andhydro-processed to form the base stock.

BACKGROUND

This section is intended to introduce various aspects of the art, whichmay be associated with examples of the present techniques. Thisdescription is believed to assist in providing a framework to facilitatea better understanding of particular aspects of the present techniques.Accordingly, it should be understood that this section should be read inthis light, and not necessarily as admissions of prior art.

High molecular weight paraffins suitable for the production of highquality lube base stock and distillate fuel may be in short supply andexpensive to manufacture. In addition, the oligomerization of olefins istypically performed with high purity feed streams, such as polymer gradeethylene.

The production of higher molecular weight linear paraffins andisoparaffins, for example, to form base stocks, from hydrocarbon streamsmay involve numerous steps, which affect the costs for the finalproducts. One example of the production of these compounds is theproduction of syngas, CO and H₂ by steam reforming of methane, followedby methanol synthesis. The methanol may then be converted to olefins viaa methane-to-olefins (MTO) process. The olefins are further oligomerizedto higher molecular weight hydrocarbons. In another example, syngas isproduced for use in Fischer-Tropsch reactions which preferentiallysynthesize linear high molecular weight products. However, these optionsmay be economically problematic due to the need to first produce syngas.

Some previous research activities have focused on using impure ethylenefeeds to produce polyalphaolefins (PAOs). For example, U.S. PatentApplication Publication No. 2010/0249474 by Nicholas et al. discloses a“process for oligomerizing dilute ethylene.” As described in thepublication, a fluid catalytic process (FCC) may provide a diluteethylene stream, as heavier hydrocarbons are processed. The ethylene inthe dilute ethylene stream may be oligomerized using a catalyst, such asan amorphous silica-alumina base with a Group VIII or VIB metal that isresistant to feed impurities such as hydrogen sulfide, carbon oxides,hydrogen and ammonia. About 40 wt. %, or greater, of the ethylene in thedilute ethylene stream can be converted to heavier hydrocarbons.

Further, U.S. Patent Application Publication No. 2014/0275669 by Daage,et al, discloses the “production of lubricant base oils from diluteethylene feeds.” As described in this publication, a dilute ethylenefeed, for example, formed while cracking heavier hydrocarbons, may beoligomerized to form oligomers for use as fuels or lubricant base oils.The oligomerization of the impure dilute ethylene is performed with azeolitic catalyst. The zeolitic catalyst is resistant to the presence ofpoisons such as sulfur and nitrogen in the ethylene feed. Diluents suchas light paraffins, may be present without interfering with the process.

The feed used for both processes described above is derived from theprocessing of oil in a fluid catalytic cracker (FCC). In an FCC, heavierhydrocarbons, such as crude oil fractions with a molecular weight ofabout 300 to about 600, or higher, are contacted with a catalyst at hightemperatures to form lower molecular weight compounds. The byproductgases from the FCC include olefins that may be used to form theoligomers.

The oligomerization of blends of ethylene with co-monomers, such as1-hexene, 1-heptene, 1-octene, 1-dodecene, and 1-hexadecene, has beenexplored. For example, U.S. Pat. No. 7,238,764 describes a process forthe co-oligomerization of ethylene and alpha olefins. Theco-oligomerization of the alpha olefins with ethylene is performed inthe presence of a metal catalyst system. The metal catalyst system mayinclude bis-aryliminepyridine MXa complexes, [bis-aryliminepyridineMY_(p).L_(b) ⁺][NC⁻]_(q) complexes, or both. The process is carried outin an ethylene pressure of less than about 2.5 megapascals (MPa).

SUMMARY

In an embodiment, the present invention provides a system formanufacturing a base stock from an ethanol stream. The system includes adehydration reactor configured to form an impure ethylene stream fromthe ethanol stream, a recovery system configured to purify the impureethylene stream to form an ethylene stream, and an oligomerizationreactor configured to oligomerize the ethylene stream to form a rawoligomer stream. A distillation column is configured to separate a lightolefinic stream from the raw oligomer stream, wherein the light olefinicstream is blended with the ethylene stream to form a blended stream, andthe blended stream is provided to the oligomerization reactor. Thedistillation column is also configured to separate an intermediateolefinic stream, and a heavy olefinic stream from the raw oligomerstream. A hydro-processing system is configured to hydroprocess theheavy olefinic stream to form a hydroprocessed stream. A productdistillation column is configured to separate the hydroprocessed streamto form the base stock.

In another embodiment, the present invention provides a method formanufacturing a base stock from an ethanol stream. The method includesdehydrating an ethanol stream to form an impure ethylene stream,recovering an ethylene stream from the impure ethylene stream, andoligomerizing the ethylene stream to form a raw oligomer stream. A lightolefinic stream is distilled from the raw oligomer stream and blendedinto the ethylene stream prior to the oligomerization. A heavy olefinicstream is distilled from the raw oligomer stream, and hydro-processed toform a hydro-processed stream. The hydroprocessed stream is distilled toform the base stock.

In another embodiment, the present invention discloses a system formanufacturing a base oil stock from ethanol. The system includes adehydration reactor configured to form an impure ethylene stream from anethanol stream. A recovery system is configured to form an ethylenestream from the impure ethylene stream. An oligomerization reactor isconfigured to convert the ethylene stream to a raw olefinic stream bycontacting the ethylene stream with a homogeneous catalyst. Adistillation column is configured to separate a light olefinic streamand a heavy olefinic stream from the raw olefinic stream and the lightolefinic stream is combined with the ethylene stream to theoligomerization reactor. A hydro-processing system is configured tohydroprocess the heavy olefinic stream to form a hydroprocessed stream.The hydroprocessed stream may be demetallated, hydrocracked, orhydroisomerized, or any combination thereof.

DESCRIPTION OF THE DRAWINGS

The advantages of the present techniques are better understood byreferring to the following detailed description and the attacheddrawings.

FIG. 1(A) is a simplified block diagram of a system for producing basestocks from an ethanol feed, in accordance with examples.

FIG. 1(B) is a simplified block diagram of a recovery system forpurifying an impure ethylene stream formed from the dehydration ofethanol, in accordance with examples.

FIG. 2 is a simplified block diagram of another system for producingbase stocks from an ethanol feedstock, in accordance with examples.

FIG. 3 is a process flow diagram of a method for producing base stocksfrom an ethanol feedstock, in accordance with examples.

FIG. 4 is a drawing of related homogeneous catalysts, having differentligands, that may be used for the oligomerization or dimerizationprocesses, in accordance with examples.

FIG. 5 is a plot of the Schultz-Flory distribution of a product thatincludes different carbon numbers, in accordance with examples.

FIG. 6 is a plot of the effect of the change in carbon numbercomposition on a weight fraction of a product as the Schultz-Florydistribution changes, in accordance with examples.

FIGS. 7(A) and 7(B) are plots of gas chromatograms illustrating thechanges caused by dimerization of an alpha olefin mixture, in accordancewith examples.

FIGS. 8(A) and 8(B) are plots of gas chromatograms illustrating thechanges caused by hydroisomerization of an alpha olefin mixture, inaccordance with examples.

FIG. 9 is a plot of DEPT-135 C-13 NMR spectra illustrating the changescaused by hydroisomerization of an alpha olefin mixture, in accordancewith examples.

DETAILED DESCRIPTION

In the following detailed description section, specific examples of thepresent techniques are described. However, to the extent that thefollowing description is specific to a particular example or aparticular use of the present techniques, this is intended to be forexemplary purposes only and simply provides a description of theexemplary examples. Accordingly, the techniques are not limited to thespecific examples described below, but rather, include all alternatives,modifications, and equivalents falling within the true spirit and scopeof the appended claims.

As renewable feedstock becomes more abundant the biological productionof ethanol, termed bioethanol herein, may provide a significant sourceof feedstocks for hydrocarbon products. The process described hereinallows the coproduction of high quality (Group III) base stock andlinear alpha olefins from a renewable feedstock, such as bioethanol. Theprocess begins with the production of ethylene from bioethanol throughcatalytic dehydration. The ethylene is purified, for example to removethe water from the dehydration, among other contaminants. The purifiedethylene stream is then introduced to a reaction zone in anoligomerization reactor where a homogeneous catalyst, for example, asdescribed with respect to FIG. 4, is used to generate linearalpha-olefins (LAOS) with a Schulz-Flory (S-F) distribution.

As used herein, a “catalyst” is a material that increases the rate ofspecific chemical reactions under certain conditions of temperature andpressure. Catalysts may be heterogeneous, homogenous, and bound. Aheterogeneous catalyst is a catalyst that has a different phase from thereactants. The phase difference may be in the form of a solid catalystwith liquid or gaseous reactants or in the form of immiscible phases,such as an aqueous acidic catalyst suspended in droplets in an organicphase holding the reactants. A heterogeneous catalyst may be bound, suchas a zeolite bound with alumina or another metal oxide. A homogeneouscatalyst is soluble in the same phase as the reactants, such as anorganometallic catalyst dissolved in an organic solvent with a reactant.

As used herein, “base stock” or “base oil stock” refers to hydrocarbonsthat may include paraffins, isoparaffins, napthenes, and aromaticcompounds in the lubricant range of molecular weights. The base stocksmay include semi-synthetic or synthetic feedstocks such as linearparaffins and isoparaffins in a lubricant range of molecular weights, inaddition to highly branched molecules useful for chemical applications,such as hydrocarbon fluids. Group I base stocks or base oils are definedas base oils with less than 90 wt. % saturated molecules and/or at least0.03 wt. % sulfur content. Group I base stocks also have a viscosityindex (VI) of at least 80 but less than 120. Group II base stocks orbase oils contain at least 90 wt. % saturated molecules and less than0.03 wt. % sulfur. Group II base stocks also have a viscosity index ofat least 80 but less than 120. Group III base stocks or base oilscontain at least 90 wt. % saturated molecules and less than 0.03 wt. %sulfur, with a viscosity index of at least 120. Other hydrocarbons thatmay be produced with base stocks include gasoline, diesel fuels,distillates, and other hydrocarbon fluids.

Further, the base stocks may be referred to as light neutral (LN),medium neutral (MN), and heavy neutral (HN), for example, as determinedby viscosity. The term “neutral” generally indicates the removal of mostnitrogen and sulfur atoms to lower reactivity in the final oil. The basestocks are generally classified by viscosity, measured at 100° C. as akinematic viscosity under the techniques described in ASTM D445. Theviscosity may be reported in millimeters{circumflex over ( )}2/second(centistokes, cSt). The base stocks may also be classified by boilingpoint range, for example, determined by simulated distillation on a gaschromatograph, under the techniques described in ASTM D 2887. It shouldbe noted that the viscosity ranges and boiling point ranges describedherein are merely examples, and may change, depending on the content oflinear paraffins, branched paraffins, cyclic hydrocarbons, and the like.A light neutral base stock may have a kinematic viscosity of about 4 cStto about 6 cSt and may have a boiling point range of about 380° C. toabout 450° C. A medium neutral base stock may have a kinematic viscosityof about 6 cSt to about 10 cSt and a boiling point range of about 440°C. to about 480° C. A heavy neutral base stock may have a kinematicviscosity of about 10 cSt to about 20 cSt, or higher, and a boilingpoint range of about 450° C. to about 565° C.

The oligomerization reaction forms oligomers by reacting small moleculeolefins, such as ethylene and propylene, termed monomers, to form ashort chain or oligomer. The oligomers may include two to 50 monomers,or more, depending on the reaction conditions used. The oligomers may belinear alpha-olefins with a Schulz-Flory (S-F) distribution. As usedherein, an S-F distribution is a probability distribution that describesthe relative ratios of oligomers of different lengths that occur in anideal step-growth oligomerization process. Generally, shorter oligomersare favored over longer oligomers.

However, the S-F distribution of the olefinic products may be controlledby the selection of an organic ligand on the catalyst, or through theselection of reaction conditions such as temperature and pressure. Thesechoices may be used to enhance the production of either light LAOs orheavier, base stock range molecules. The product olefins may then besplit into light olefinic (C12−), medium olefinic (C12-C22), and heavyolefinic (C24+) fractions, for example, through conventionaldistillation. It may be noted that the olefinic fractions may not bepure olefins, but may include other compounds with similar boilingpoints, such as paraffinic compounds. The light fraction may include C4,C6, C8, C10, and C12 LAOS, the medium fraction may be sent to adimerization or alkylation reactor using a catalyst selected from avariety of heterogeneous or homogeneous catalysts, and the heavyfraction may be sent to a demetallation zone or stage then to ahydrocracking/hydroisomerization (HDC/HDI) reactor to produce the highquality (Group III) base stock.

The ability to control the S-F distribution makes the targetedproduction of particular products possible. In some examples, an S-Fdistribution of about 0.75 to about 0.91 is targeted to make various waxand base stock products with carbon numbers of at least 24. In otherexamples, an S-F distribution of about 0.83 to about 0.87 is targeted tomake products having about 24 to about 50 carbon atoms, such as lowerviscosity base stocks. In further examples, an S-F distribution of about0.6 to about 0.75 is targeted to make products having about four toabout 22 carbon atoms, such as various linear alpha olefins. Therelation of S-F distribution to various carbon numbers is discussed withrespect to FIG. 6.

For ease of reference, certain terms used in this application and theirmeanings as used herein are set forth. To the extent a term is notdefined herein, it should be given the broadest definition persons inthe pertinent art have given that term as reflected in at least oneprinted publication or issued patent. Further, the present techniquesare not limited by the usage of the terms shown herein, as allequivalents, synonyms, new developments, and terms or techniques thatserve the same or a similar purpose are considered to be within thescope of the present claims.

FIG. 1(A) is a simplified block diagram of a system 100 for producingbase stocks from an ethanol feed, in accordance with examples. Theprocess begins with the introduction of the ethanol feed stream 102 to adehydration reactor 104. As sourced from a fermentation process andpurified by distillation, the ethanol feed stream 102 may contain 4.6wt. % water as an azeotropic mixture. Depending on the process used toproduce the ethanol feed stream 102, other treatments may be used forpurification including, for example, filtration, distillation, membranepurification, and the like.

Dehydration

In the dehydration reactor 104, the ethanol feed stream 102 may bevaporized and contacted with a solid acid catalyst, such as γ-Al2O3based, molecular sieve (HZSM-5 zeolites), and heteropoly acid, at150−500° C. and 1-50 bar pressure. These catalysts can be modified withother metal oxides (e.g., MgO/SiO2) and doped with chemical elements(e.g., La/P), resulting in varying lifetime, conversion of ethanol, andselectivity for ethylene to form a raw ethylene stream 106. The mixtureof products in the raw ethylene stream 106 from the dehydration reactor104 may include ethylene, water, diethylether, and small amounts ofother materials, for example, acetaldehyde, hydrogen and lighthydrocarbons.

A separation system 108 may be used to separate the water formed in thedehydration process from the raw ethylene stream 106 to form anoligomerization feed stream 110. The separation system 108 may include acondenser to remove water, as described with respect to FIG. 1(B), acaustic column, or a dryer, forming the oligomerization feed stream 110.After water removal, the oligomerization feed stream 110 may include,for example, about 95% ethylene, about 99% ethylene, or higher, theimpurities being hydrogen, methane, ethane, or propane.

Oligomerization

The oligomerization feed stream 110 is provided to an oligomerizationreactor 112, where it may be contacted with a homogenous catalyst 114,for example, an organometallic catalyst. In examples described herein,the homogenous catalyst 114 is generally an impurity toleranthomogeneous catalyst, such as an Iron (II) pyridine-bis-imide (Fe—PBI),capable of the oligomerization of the oligomerization feed stream 110 toC10+ products, C25+, or C50+ products, to produce diesel, lube, andhydrocarbon fluid molecules, such as the base stocks.

An example of a homogenous catalyst that may be includes an iron (II)pyridine-bis-imine (Fe—PBI) compound having a structure of formula 1:

In formula 1, X is a halogen or hydrocarbyl radical, such as Cl. Each Rsubstituent is independently a halogen or hydrocarbyl radical, and eachn is an integer from 1-5 representing the number of R groups present.Each n is 1, 2 or 3. In some examples, n is 2 or 3. Each R is a C1-C10alkyl, or a halogen. In some examples, R is methyl, ethyl or n-propyl.In some examples, at least one R is methyl. In some examples, at leastone R is fluorine. In some examples, Rn comprises one, two, or threesubstituents, wherein each of the substituents is methyl, or fluorine.Each R^(a), and R^(b) are independently a hydrogen, halogen orhydrocarbyl radical. In some examples, each R^(a) is a hydrocarbyl orhydrogen, or a hydrogen. Each R^(b) is a hydrocarbyl, such as a C1-C10alkyl, or methyl.

The homogenous catalyst may include an iron (II) pyridine-bis-imine(Fe—PBI) compound having a structure of formula 2:

In formula 2, each R^(a), R^(b) and X are as defined above, and each Ais independently a substituted aryl group including one, two or three Rsubstituents as defined above.

In some examples, each A is defined by a structure shown in formula 3:

In formula 3, the one position of the phenyl ring is bonded to thenitrogen of the iron (II) pyridine-bis-imine complex, and each R², R³,R⁴, R⁵, and R⁶ are independently C1 to C10 alkyl, halogen or hydrogenradical. In some examples, each R², R³, R⁴, R⁵, and R⁶ are independentlymethyl, ethyl, n-propyl, fluoro, and hydrogen. In some examples, eachR², R³, R⁴, R⁵, and R⁶ are independently methyl, fluoro and hydrogen. Insome examples, each R² is methyl and each R⁶ is fluoro. In someexamples, each R² is fluoro and each R⁴ is methyl. In some examples,each R² and R⁶ are methyl, and each R⁴ is fluoro. In some examples, eachR² is methyl and each R⁴ is fluoro. In some examples, each R² is methyl.Examples of homogenous catalysts that may be used for theoligomerization are discussed further with respect to FIG. 4. In someexamples, the organometallic catalysts may be supported to formheterogeneous catalysts.

Generally, the homogeneous catalysts are activated. After the complexeshave been synthesized, catalyst systems may be formed by combining themwith activators in any manner known from the literature, including bysupporting them for use in slurry or gas phase polymerization reactions.The catalyst systems may also be added to or generated in solutionpolymerization or bulk polymerization (in the monomer). The catalystsystem typically includes a complex as described above and an activatorsuch as alumoxane or a non-coordinating anion. Activation may beperformed using alumoxane solution including methyl alumoxane, referredto as MAO, as well as modified MAO, referred to herein as MMAO,containing some higher alkyl groups to improve the solubility.Particularly useful MAO can be purchased from Albemarle, typically in a10 wt. % solution in toluene. In some embodiments, the catalyst systemuses an activator selected from alumoxanes, such as methyl alumoxane,modified methyl alumoxane, ethyl alumoxane, iso-butyl alumoxane, and thelike.

When an alumoxane or modified alumoxane is used, thecomplex-to-activator molar ratio is from about 1:3000 to 10:1; or from1:2000 to 10:1; or from 1:1000 to 10:1; or from 1:500 to 1:1; or from1:300 to 1:1; or from 1:200 to 1:1; or from 1:100 to 1:1; or from 1:50to 1:1; or from 1:10 to 1:1. When the activator is an alumoxane(modified or unmodified), some examples select the maximum amount ofactivator at a 5000-fold molar excess over the catalyst precursor (permetal catalytic site). The preferred minimum activator-to-complex ratiois 1:1 molar ratio.

Activation may also be performed using non-coordinating anions, (NCAs),of the type described in European Patent Application Nos. 277 003 A1 and277 004 A1. An NCA may be added in the form of an ion pair using, forexample, [DMAH]+[NCA]− in which the N,N-dimethylanilinium (DMAH) cationreacts with a basic leaving group on the transition metal complex toform a transition metal complex cation and [NCA]−. The cation in theprecursor may, alternatively, be trityl. Alternatively, the transitionmetal complex may be reacted with a neutral NCA precursor, such asB(C₆F₅)₃, which abstracts an anionic group from the complex to form anactivated species. Useful activators include N,N-dimethylaniliniumtetrakis (pentafluorophenyl)borate (i.e., [PhNMe₂H]B(C₆F₅)₄) andN,N-dimethylanilinium tetrakis (heptafluoronaphthyl)borate, where Ph isphenyl, and Me is methyl.

Additionally, activators useful herein include those described in U.S.Pat. No. 7,247,687 at column 169, line 50 to column 174, line 43,particularly column 172, line 24 to column 173, line 53. These areincorporated by reference herein.

Non-coordinating anion (NCA) is defined to mean an anion either thatdoes not coordinate to the catalyst metal cation or that does coordinateto the metal cation, but only weakly. The term NCA is also defined toinclude multicomponent NCA-containing activators, such as

N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain anacidic cationic group and the non-coordinating anion.

The term NCA also includes neutral Lewis acids, such astris(pentafluorophenyl)boron, that can react with a catalyst to form anactivated species by abstraction of an anionic group. An NCA coordinatesweakly enough that a neutral Lewis base, such as an olefinically oracetylenically unsaturated monomer can displace it from the catalystcenter. Any metal or metalloid that can form a compatible, weaklycoordinating complex may be used or contained in the noncoordinatinganion. Suitable metals include, but are not limited to, aluminum, gold,and platinum. Suitable metalloids include, but are not limited to,boron, aluminum, phosphorus, and silicon. A stoichiometric activator canbe either neutral or ionic. The terms ionic activator, andstoichiometric ionic activator can be used interchangeably. Likewise,the terms neutral stoichiometric activator, and Lewis acid activator canbe used interchangeably. The term non-coordinating anion includesneutral stoichiometric activators, ionic stoichiometric activators,ionic activators, and Lewis acid activators.

In an example described herein, the non-coordinating anion activator isrepresented by the following formula (1):(Z)_(d) ⁺(A^(d−))  (1)wherein Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base;H is hydrogen and (L-H)⁺ is a Bronsted acid; A^(d−) is anon-coordinating anion having the charge d−; and d is an integer from 1to 3.

When Z is (L-H) such that the cation component is (L-H)d+, the cationcomponent may include Bronsted acids such as protonated Lewis basescapable of protonating a moiety, such as an alkyl or aryl, from thecatalyst precursor, resulting in a cationic transition metal species, orthe activating cation (L-H)d+ is a Bronsted acid, capable of donating aproton to the catalyst precursor resulting in a transition metal cation,including ammoniums, oxoniums, phosphoniums, silyliums, and mixturesthereof, or ammoniums of methylamine, aniline, dimethylamine,diethylamine,

N-methylaniline, diphenylamine, trimethylamine, triethylamine,N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromoN,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums fromtriethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniumsfrom ethers, such as dimethyl ether diethyl ether, tetrahydrofuran, anddioxane, sulfoniums from thioethers, such as diethyl thioethers andtetrahydrothiophene, and mixtures thereof.

When Z is a reducible Lewis acid, it may be represented by the formula:(Ar₃C+), where Ar is aryl or aryl substituted with a heteroatom, or a C₁to C₄₀ hydrocarbyl, the reducible Lewis acid may be represented by theformula: (Ph₃C+), where Ph is phenyl or phenyl substituted with aheteroatom, and/or a C1 to C40 hydrocarbyl. In an example, the reducibleLewis acid is triphenyl carbenium.

Examples of the anion component Ad− include those having the formula[Mk+Qn]d− wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5 or 6, or 3, 4, 5or 6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, or boron or aluminum, and Q is independently ahydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide,hydrocarbyl radicals, said Q having up to about 20 carbon atoms with theproviso that in not more than one occurrence is Q a halide, and two Qgroups may form a ring structure. Each Q may be a fluorinatedhydrocarbyl radical having about 1 to 20 carbon atoms, or each Q is afluorinated aryl radical, or each Q is a pentafluoryl aryl radical.Examples of suitable Ad− components also include diboron compounds asdisclosed in U.S. Pat. No. 5,447,895, which is fully incorporated hereinby reference.

In an example in any of the NCAs represented by Formula 1 describedabove, the anion component Ad− is represented by the formula[M*k*+Q*n*]d*− wherein k* is 1, 2, or 3; n* is 1, 2, 3, 4, 5, or 6 (or1, 2, 3, or 4); n*−k*=d*; M* is boron; and Q* is independently selectedfrom hydride, bridged or unbridged dialkylamido, halogen, alkoxide,aryloxide, hydrocarbyl radicals, said Q* having up to about 20 carbonatoms with the proviso that in not more than 1 occurrence is Q* ahalogen.

The techniques describe herein also relate method to dimerize olefinsincluding contacting olefins (such as ethylene, butene, hexane, andothers) with a catalyst complex as described above and an NCA activatorrepresented by the Formula (2):R_(n)M**(ArNHal)_(4-n)  (2)where R is a monoanionic ligand; M** is a Group 13 metal or metalloid;ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclicaromatic ring, or aromatic ring assembly in which two or more rings (orfused ring systems) are joined directly to one another or together; andn is 0, 1, 2, or 3. Typically the NCA including an anion of Formula 2also includes a suitable cation that is essentially non-interfering withthe ionic catalyst complexes formed with the transition metal compounds,or the cation is Z_(d) ⁺ as described above.

In an example, in any of the NCAs including an anion represented byFormula 2 described above, R is selected from the group consisting of C₁to C₃₀ hydrocarbyl radicals. In an example, C₁ to C₃₀ hydrocarbylradicals may be substituted with one or more C₁ to C₂₀ hydrocarbylradicals, halide, hydrocarbyl substituted organometalloid, dialkylamido,alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido,arylphosphide, or other anionic substituent; fluoride; bulky alkoxides,where bulky means C₄ to C₂₀ hydrocarbyl radicals; —SRa, —NR^(a) ₂, and—PR^(a) ₂, where each R^(a) is independently a monovalent C₄ to C₂₀hydrocarbyl radical including a molecular volume greater than or equalto the molecular volume of an isopropyl substitution or a C₄ to C₂₀hydrocarbyl substituted organometalloid having a molecular volumegreater than or equal to the molecular volume of an isopropylsubstitution.

In an example, in any of the NCAs including an anion represented byFormula 2 described above, the NCA also includes cation including areducible Lewis acid represented by the formula: (Ar₃C+), where Ar isaryl or aryl substituted with a heteroatom, and/or a C₁ to C₄₀hydrocarbyl, or the reducible Lewis acid represented by the formula:(Ph₃C+), where Ph is phenyl or phenyl substituted with one or moreheteroatoms, and/or C₁ to C₄₀ hydrocarbyls.

In an example in any of the NCAs including an anion represented byFormula 2 described above, the NCA may also include a cation representedby the formula, (L-H)d+, wherein L is an neutral Lewis base; H ishydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, or (L-H)d+ is aBronsted acid selected from ammoniums, oxoniums, phosphoniums,silyliums, and mixtures thereof.

Further examples of useful activators include those disclosed in U.S.Pat. Nos. 7,297,653 and 7,799,879, which are fully incorporated byreference herein.

In an example, an activator useful herein includes a salt of a cationicoxidizing agent and a non-coordinating, compatible anion represented bythe Formula (3):(OX^(e+))_(d)(A^(d−))_(e)  (3)wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis 1, 2 or 3; d is 1, 2 or 3; and A^(d−) is a non-coordinating anionhaving the charge of d−(as further described above). Examples ofcationic oxidizing agents include: ferrocenium, hydrocarbyl-substitutedferrocenium, Ag⁺, or Pb⁺². Suitable examples of A^(d−) includetetrakis(pentafluorophenyl)borate.

Activators useful in catalyst systems herein include: trimethylammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl) borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, and the types disclosed in U.S. Pat.No. 7,297,653, which is fully incorporated by reference herein.

Suitable activators also include: N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, [Ph3C+][B(C6F5)4−],[Me3NH+][B(C6F5)4−];1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium;and tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In an example, the activator includes a triaryl carbonium (such astriphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl) borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenyl carbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl) phenyl)borate).

In an example, two NCA activators may be used in the polymerization andthe molar ratio of the first NCA activator to the second NCA activatorcan be any ratio. In an example, the molar ratio of the first NCAactivator to the second NCA activator is 0.01:1 to 10,000:1, or 0.1:1 to1000:1, or 1:1 to 100:1.

In an example, the NCA activator-to-catalyst ratio is a 1:1 molar ratio,or 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to 500:1 or 1:1 to 1000:1.In an example, the NCA activator-to-catalyst ratio is 0.5:1 to 10:1, or1:1 to 5:1.

In an example, the catalyst compounds can be combined with combinationsof alumoxanes and NCAs (see for example, U.S. Pat. Nos. 5,153,157;5,453,410; European Patent Application No. EP 0 573 120 B1; WIPO PatentPublication No. WO 94/07928; and WIPO Patent Publication No. WO 95/14044which discuss the use of an alumoxane in combination with an ionizingactivator, all of which are incorporated by reference herein).

In an example, when an NCA (such as an ionic or neutral stoichiometricactivator) is used, the complex-to-activator molar ratio is typicallyfrom 1:10 to 1:1; 1:10 to 10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1;1:2 to 1.2:1; 1:2 to 10:1; 1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to1.2:1; 1:3 to 10:1; 1:3 to 2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1:1; 1:5to 10:1; 1:5 to 2:1; 1:5 to 3:1; 1:5 to 5:1; 1:1 to 1:1.2.

Alternately, a co-activator or chain transfer agent, such as a group 1,2, or 13 organometallic species (e.g., an alkyl aluminum compound suchas tri-n-octyl aluminum), may also be used in the catalyst systemherein. The complex-to-co-activator molar ratio is from 1:100 to 100:1;1:75 to 75:1; 1:50 to 50:1; 1:25 to 25:1; 1:15 to 15:1; 1:10 to 10:1;1:5 to 5:1; 1:2 to 2:1; 1:100 to 1:1; 1:75 to 1:1; 1:50 to 1:1; 1:25 to1:1; 1:15 to 1:1; 1:10 to 1:1; 1:5 to 1:1; 1:2 to 1:1; 1:10 to 2:1.

When the catalyst compounds are ligated metal dihalide compounds, aco-activator is always used when an NCA activator is used.

Other catalysts, including heterogeneous catalyst such as zeolites, maybe used for the oligomerization. However, the oligomerization processmay not be as clean, e.g., producing more isomers and fewer linear alphaolefins. Zeolites that may be suitable for this conversion include, butare not limited to 10-ring zeolites such as ZSM-5 (MFI), ZSM-11 (MEL),ZSM-48 (MRE), and the like, with Si/Al₂ ratios from 5 to 500. Thezeolites are used in their proton form and may or may not be promotedwith metals by ion exchange or impregnation. In addition, the binderused during formulation can have an effect on the yield and productslate.

The oligomerization process can be performed as a single step process ora two-step process. In a single step process, all of the oligomerizationis performed in a single stage or in a single reactor in theoligomerization reactor 112. The oligomerization feed stream 110 isintroduced into the single stage generally as a gas phase feed. Theoligomerization feed stream 110 is contacted with the homogenouscatalyst 114 under effective oligomerization conditions. A solvent, suchas hexane, cyclohexane, or toluene, may be used for the oligomerizationprocess, and recycled. The ethylene feed may be contacted with thehomogenous catalyst 114 at a temperature of 20° C. to 300° C. In someexamples, the reaction temperature is at least 25° C., or at least 50°C., or at least 100° C., and is 250° C. or less, or 225° C. or less. Thetotal pressure can be from 1 atm (100 kPa) to 200 atm (20.2 MPa). Insome examples, the total pressure is 100 atm (10.1 MPa) or less. In someexamples, the oligomerization feed is contacted with the catalyst at ahydrogen partial pressure that is at least 1% of the total pressure,such as at least 5% of the total pressure or at least 10% of the totalpressure or up to about 50% on a volumetric basis. The reaction forms araw oligomer stream 116 that can then be fractionated in a distillationcolumn 118. An optional step of to quench the catalyst may be used,which consists of using a base, either aqueous or organic, before thefractionation.

In the distillation column 118, three streams may be separated from theraw oligomer stream 116. These may include a light olefinic stream 120,an intermediate olefinic stream 122 and a heavy olefinic stream 124. Itmay be noted that the olefinic streams 120, 122, and 124 may not becomposed of 100% olefinic compounds, but may include a number of othercompounds, such as paraffin, that are removed in the same boiling pointranges as the olefinic compounds.

The light olefinic stream 120 may include, for example, linearalpha-olefins having from about four carbon atoms to about 10 carbonatoms and unreacted ethylene. Further, as higher molecular weightcompounds are formed, the amounts of paraffinic compounds may increaseas well. In this example, the light olefinic stream 120 is combined withthe oligomerization feed stream 110 and provided to the oligomerizationreactor 112 as combined stream 126.

The intermediate olefinic stream 122 may be provided to a dimerizationreactor 128. As an example, the intermediate olefinic stream 122 mayinclude compounds having about 12 carbon atoms to compounds having about22 carbon atoms, although this may be adjusted based, at least in part,on the takeoff point in the distillation column 118. In the dimerizationreactor 128, the intermediate olefinic stream 122 may be contacted witha homogeneous or heterogeneous catalyst to be dimerized to form aproduct that includes carbon compounds having about 24 carbon atoms toabout 44 carbon atoms. The reaction may be run at a temperature of about50° C. to about 400° C., and a pressure of about 50 psig to about 2000psig. The dimerized stream 130 may be returned to the distillationcolumn 118, in which lower carbon number compounds, such as unreactedcompounds having about 12 carbon atoms to about 22 carbon atoms, may besent back to the dimerization reactor 128 for further processing.

The heavy olefinic stream 124 may have at least about 24 carbon atoms.To lower the amounts of contaminants, as well as to upgrade the finalproducts, the heavy olefinic stream 124 may be provided to ahydro-processing reactor 132 to remove contaminants and improve productproperties, such as cold flow properties. For example, hydrotreatment ormild hydrocracking can be used for removal of contaminants, andoptionally to provide some viscosity index uplift, while hydrocrackingand hydroisomerization, termed catalytic HDC/HDI, may be used to improvecold flow properties.

Hydro-Processing

As used herein, “hydro-processing” includes any hydrocarbon processingthat is performed in the presence of hydrogen. The hydrogen may be addedto the hydro-processing reactor 132 as a hydrogen treat stream 134. Thehydrogen treat stream 134 is fed or injected into a vessel or reactionzone or hydro-processing zone in which the hydro-processing catalyst islocated. The hydrogen treat stream 134 may be pure hydrogen or ahydrogen-containing gas, which is a gas stream containing hydrogen in anamount that is sufficient for the intended reactions. The hydrogen treatstream 134 may include one or more other gasses, such as nitrogen andlight hydrocarbons, that do not interfere with or affect either thereactions or the products. Impurities, such as H₂S and NH₃ areundesirable and would typically be removed from the hydrogen treatstream 134 before it is conducted to the reactor. The hydrogen treatstream 134 introduced into a reaction stage may include at least 50 vol.% hydrogen or at least 75 vol. % hydrogen. The products of thehydro-processing system 132, termed a hydro-processed stream 136, mayhave lower contaminants, including metals and heteroatom compounds, aswell as improved viscosities, viscosity indices, saturates content, lowtemperature properties, volatilities and depolarization, and the like.

Various types of hydro-processing can be used in the production of fuelsand base stocks, such as hydroconversion, hydrocracking, hydrogenation,hydrotreating, hydrodesulfurization, hydrodenitrogenation,hydrodemetallation, and hydroisomerization, among others. Typicalprocesses include a demetallation process to remove metallic remnants ofthe catalyst. Further, a catalytic dewaxing, orhydrocracking/hydroisomerization (HDC/HDI) process, may be included tomodify viscosity properties or cold flow properties, such as pour pointand cloud point. The hydrocracked or dewaxed feed can then behydrofinished, for example, to saturate olefins and aromatics from theheavy olefinic stream 124. In addition to the above, a hydrotreatmentstage can also be used for contaminant removal. The hydrotreatment ofthe oligomer feed to remove contaminants may be performed prior to orafter the hydrocracking or the HDC/HDI.

In the discussion below, a stage in a hydro-processing system 132 cancorrespond to a single reactor or a plurality of reactors. In someexamples, multiple reactors can be used to perform one or more of theprocesses, or multiple parallel reactors can be used for all processesin a stage. Each stage or reactor may include one or more catalyst bedscontaining hydro-processing catalyst. Note that a catalyst bed in thediscussion below may refer to a partial physical catalyst bed. Forexample, a catalyst bed within a reactor could be filled partially witha hydrocracking catalyst and partially with an HDC/HDI catalyst. Forconvenience in description, even though the two catalysts may be stackedtogether in a single catalyst bed, the hydrocracking catalyst and theHDC/HDI catalyst can each be referred to conceptually as separatecatalyst beds. As an example, the hydro-processing system 132 shown inFIG. 1 includes a demetallation system 132A and ahydrocracking/hydroisomerization (HDC/HDI) system 132B, shown asseparate reactors or units.

Hydrodemetallation

The demetallation system 132A includes a demetallation catalyst andoperates at about 200-500° C. and 50-1200 psi. The demetallation systemremoves metals in the homogeneous catalyst, such as Fe and Al, from theorganic components, which are deposited on the solid catalysts. Thedemetallation system is typically used for the removal of metals inpetroleum oil. The metals in petroleum oil exist as metal complexes,much like the metals in the homogeneous catalysts. The hydrogen treatstream 134 may be added to each of the stages or reactors separately, ormay be added in fewer additions, such as to each reactor, or only afirst reactor.

Hydroisomerization/Hydrocracking (HDC/HDI)

In the HDC/HDI system 132B, suitable HDC/HDI (dewaxing) catalysts mayinclude molecular sieves such as crystalline aluminosilicates, orzeolites. In various examples, the molecular sieve includes ZSM-5,ZSM-22, ZSM-23, ZSM-35, ZSM-48, SAPO-11, zeolite Beta, or zeolite Y, orincludes combinations thereof, such as ZSM-23 and ZSM-48, or ZSM-48 andzeolite Beta. Molecular sieves that are selective for dewaxing byisomerization, as opposed to cracking, may be used, such as ZSM-48,ZSM-23, SAPO-11 or any combinations thereof. The molecular sieves mayinclude a 10-member ring 1-D molecular sieve. Examples include EU-1,ZSM-35 (or ferrierite), ZSM-11, ZSM-57, NU-87, SAPO-11, ZSM-48, ZSM-23,and ZSM-22. Some of these materials may be more efficient, such as EU-2,EU-11, ZBM-30, ZSM-48, or ZSM-23. Note that a zeolite having the ZSM-23structure with a silica to alumina ratio of from 20:1 to 40:1 may bereferred to as SSZ-32. Other molecular sieves that are isostructuralwith the above materials include Theta-I, NU-10, EU-13, KZ-1, and NU-23.The HDC/HDI catalyst may include a binder for the molecular sieve, suchas alumina, titania, silica, silica-alumina, zirconia, or a combinationthereof, for example alumina and titania or silica and zirconia,titania, or both.

In various examples, the catalysts may include a hydrogenation catalystto saturate multiple bonds and aromatics, which may be termedhydrofinishing herein. The hydrogenation catalyst typically includes ametal hydrogenation component that is a Group VI and/or a Group VIIImetal. In some examples, the metal hydrogenation component is a GroupVIII noble metal. For example, the metal hydrogenation component may bePt, Pd, or a mixture thereof. Further, the metal hydrogenation componentmay be a combination of a non-noble Group VIII metal with a Group VImetal. Suitable combinations can include Ni, Co, or Fe with Mo or W, or,in some examples, Ni with Mo or W.

The metal hydrogenation component may be added to the catalyst in anyconvenient manner. For example, the metal hydrogenation component may becombined with the catalyst using an incipient wetness. In thistechnique, after combining a zeolite and a binder, the combined zeoliteand binder can be extruded into catalyst particles. These catalystparticles may then be exposed to a solution containing a suitable metalprecursor. In some examples, metal can be added to the catalyst by ionexchange, where a metal precursor is added to a mixture of zeolite (orzeolite and binder) prior to extrusion.

The amount of metal in the catalyst may be at least about 0.1 wt. %based on catalyst, or at least about 0.15 wt. %, or at least about 0.2wt. %, or at least about 0.25 wt. %, or at least about 0.3 wt. %, or atleast about 0.5 wt. % based on catalyst. The amount of metal in thecatalyst may be about 20 wt. % or less based on catalyst, or about 10wt. % or less, or about 5 wt. % or less, or about 2.5 wt. % or less, orabout 1 wt. % or less. For examples where the metal is Pt, Pd, anotherGroup VIII noble metal, or a combination thereof, the amount of metalmay be from about 0.1 to about 5 wt. %, about 0.1 to about 2 wt. %, orabout 0.25 to about 1.8 wt. %, or about 0.4 to about

1.5 wt. %. For examples where the metal is a combination of a non-nobleGroup VIII metal with a Group VI metal, the combined amount of metal maybe from about 0.5 wt. % to about 20 wt. %, or about 1 wt. % to about 15wt. %, or about 2.5 wt. % to about 10 wt. %.

The HDC/HDI catalysts may also include a binder. In some examples, theHDC/HDI catalysts may use a low surface area binder. A low surface areabinder represents a binder with a surface area of about 100 m²/g orless, or 80 m²/g or less, or about 70 m²/g or less. The amount ofzeolite in a catalyst formulated using a binder can be from about 30 wt.% zeolite to about 90 wt. % zeolite relative to the combined weight ofbinder and zeolite. In some examples, the amount of zeolite may be atleast about 50 wt. % of the combined weight of zeolite and binder, suchas at least about 60 wt. % or from about 65 wt. % to about 80 wt. %.

A zeolite can be combined with binder in any convenient manner. Forexample, a bound catalyst can be produced by starting with powders ofboth the zeolite and binder, combining and mulling the powders withadded water to form a mixture, and then extruding the mixture to producea bound catalyst of a desired size. Extrusion aids can also be used tomodify the extrusion flow properties of the zeolite and binder mixture.

Process conditions in a catalytic HDC/HDI zone in a may include atemperature of from about 200 to about 450° C., or from about 270 toabout 400° C., a hydrogen partial pressure of from about 1.8 MPag toabout 34.6 MPag (about 250 psig to about 5000 psig), or from about 4.8MPag to about 20.8 MPag, and a hydrogen circulation rate of from about35.6 m³/m³ (200 standard cubic feet of treat gas per barrel of oil.(SCF/B)) to about 1781 m³/m³ (10,000 SCF/B), or from about 178 m³/m³(1000 SCF/B) to about 890.6 m³/m³ (5000 SCF/B). In other examples, theconditions can include temperatures in the range of about 343° C. (600°F.) to about 435° C. (815° F.), hydrogen partial pressures of from about3.5 MPag-20.9 MPag (about 500 psig to 3000 psig), and hydrogen treat gasrates of from about 213 m³/m³ to about 1068 m³/m³ (1200 SCF/B to 6000SCF/B). These latter conditions may be suitable, for example, if theHDC/HDI stage is operating under sour conditions, e.g., in the presenceof high concentrations of sulfur compounds.

The liquid hourly space velocity (LHSV) can vary depending on the ratioof hydrocracking catalyst used to hydroisomerization catalyst in theHDC/HDI catalyst. Relative to the combined amount of hydrocracking andhydroisomerization catalyst, the LHSV may be from about 0.2 h⁻¹ to about10 h⁻¹, such as from about 0.5 h⁻¹ to about 5 h⁻¹ and/or from about 1h⁻¹ to about 4 h⁻¹. Depending on the ratio of hydrocracking catalyst tohydroisomerization catalyst used, the LHSV relative to only the HDC/HDIcatalyst can be from about 0.25 h⁻¹ to about 50 h⁻¹, such as from about0.5 h⁻¹ to about 20 h⁻¹, or from about 1.0 h⁻¹ to about 4.0 h⁻¹.

Hydrotreatment Conditions

Hydrotreatment may be used to reduce the sulfur, nitrogen, and aromaticcontent of the heavy olefinic stream 124, for example, removing nitrogencompounds from the oligomerization catalyst. The catalysts used forhydrotreatment may include hydro-processing catalysts that include atleast one Group VIII non-noble metal (Columns 8-10 of IUPAC periodictable), such as Fe, Co, or Ni, or Co or Ni, and at least one Group VImetal (Column 6 of IUPAC periodic table), such as Mo or W. Suchhydro-processing catalysts may include transition metal sulfides thatare impregnated or dispersed on a refractory support or carrier such asalumina or silica. The support or carrier itself typically has nosignificant or measurable catalytic activity. Substantially carrier- orsupport-free catalysts, commonly referred to as bulk catalysts,generally have higher volumetric activities than their boundcounterparts.

In addition to alumina or silica, other suitable support or carriermaterials can include, but are not limited to, zeolites, titania,silica-titania, and titania-alumina. Suitable aluminas include porousaluminas, such as gamma or eta forms, having average pore sizes fromabout 50 to about 200 Angstrom (Å), or about 75 to about 150 Å; asurface area from about 100 to about 300 m²/g, or about 150 to about 250m²/g; and a pore volume of from about 0.25 to about

1.0 cm³/g, or about 0.35 to about 0.8 cm³/g. Generally, any convenientsize, shape, or pore size distribution for a catalyst suitable forhydrotreatment of a distillate (including lubricant base oil) boilingrange feed in a conventional manner may be used. Further, more than onetype of hydro-processing catalyst can be used in one or multiplereaction vessels. A Group VIII non-noble metal, in oxide form, may bepresent in an amount ranging from about 2 wt. % to about40 wt. %, or from about 4 wt. % to about 15 wt. %. A Group VI metal, inoxide form, can typically be present in an amount ranging from about 2wt. % to about 70 wt. %, or, for bound catalysts, from about 6 wt. % toabout 40 wt. % or from about 10 wt. % to about 30 wt. %. These weightpercentages are based on the total weight of the catalyst. Suitablemetal catalysts include cobalt/molybdenum (for example, including about1-10% Co as oxide and about 10-40% Mo as oxide), nickel/molybdenum(including about 1-10% Ni as oxide and about 10-40% Co as oxide), ornickel/tungsten (including about 1-10% Ni as oxide and about 10-40% W asoxide) on alumina, silica, silica-alumina, or titania, among others.

Hydrotreating conditions can include temperatures of about 200° C. toabout 450° C., or about 315° C. to about 425° C.; pressures of about 250psig (1.8 MPag) to about 5000 psig (34.6 MPag) or about 300 psig (2.1MPag) to about 3000 psig (20.8 MPag); liquid hourly space velocities(LHSV) of about 0.1 hr⁻¹ to about 10 hr⁻¹; and hydrogen treat rates ofabout 200 SCF/B (35.6 m³/m³) to 10,000 SCF/B (1781 m³/m³) or about 500(89 m³/m³) to about 10,000 SCF/B (1781 m³/m³) or about 3000 psig (3.5MPag-20.9 MPag), and hydrogen treat gas rates of from about 213 m³/m³ toabout 1068 m³/m³ (1200 SCF/B 6000 SCF/B).

Hydrofinishing and Aromatic Saturation Process

In some examples, a hydrofinishing stage, an aromatic saturation stage,or both may be used. These stages are termed finishing processes herein.Finishing processes may improve color and stability in a final productby lowering the amounts of unsaturated or oxygenated compounds in thefinal product streams. The finishing may be performed in thehydro-processing system 132 after the last hydrocracking orhydroisomerization stage. Further, the finishing may occur afterfractionation of a hydro-processed stream 136 in a product distillationcolumn 138. If finishing occurs after fractionation, the finishing maybe performed on one or more portions of the fractionated product. Insome examples, the entire effluent from the last hydrocracking orHDC/HDI process can be finished prior to fractionation into individualproduct streams.

In some situations, the finishing processes, including hydrofinishingand aromatic saturation, may refer to a single process performed usingthe same catalyst. Alternatively, one type of catalyst or catalystsystem can be provided to perform aromatic saturation, while a secondcatalyst or catalyst system can be used for hydrofinishing. Typicallythe finishing processes will be performed in a separate reactor from theHDC/HDI or hydrocracking processes to facilitate the use of a lowertemperature for the finishing processes. However, an additionalhydrofinishing reactor following a hydrocracking or HDC/HDI process, butprior to fractionation, may still be considered part of a second stageof a reaction system conceptually.

Finishing catalysts can include catalysts containing Group VI metals,Group VIII metals, and mixtures thereof. In an example, the metals mayinclude a metal sulfide compound having a strong hydrogenation function.The finishing catalysts may include a Group VIII noble metal, such asPt, Pd, or a combination thereof. The mixture of metals may also bepresent as bulk metal catalysts wherein the amount of metal is 30 wt. %or greater based on the catalyst. The metals and metal compounds may bebound, for example, on a metal oxide. Suitable metal oxide supportsinclude low acidic oxides such as silica, alumina, silica-aluminas ortitania, or, in some examples, alumina.

The catalysts for aromatic saturation may include at least one metalhaving relatively strong hydrogenation function on a porous support.Typical binding materials include amorphous or crystalline oxidematerials such as alumina, silica, and silica-alumina. The bindingmaterials may also be modified, such as by halogenation or fluorination.The metal content of the catalyst may be as high as 20 wt. % fornon-noble metals. In an example, a hydrofinishing catalyst may include acrystalline material belonging to the M41S class or family of catalysts.The M41S family of catalysts are mesoporous materials having high silicacontent. Examples include MCM-41, MCM-48 and MCM-50. Examples includeMCM-41, MCM-48, MCM-49, and MCM-50. Other catalysts that may be usedinclude Beta, Y, and other large pore zeolites (12-member ring MR andup). If separate catalysts are used for aromatic saturation andhydrofinishing, an aromatic saturation catalyst can be selected based onactivity or selectivity for aromatic saturation, while a hydrofinishingcatalyst can be selected based on activity for improving productspecifications, such as product color and polynuclear aromaticreduction.

Hydrofinishing conditions can include temperatures from about 125° C. toabout 425° C., or about 180° C. to about 280° C., a hydrogen partialpressure from about 500 psig (3.4 MPa) to about 3000 psig (20.7 MPa), orabout 1500 psig (10.3 MPa) to about 2500 psig (17.2 MPa), and an LHSVfrom about 0.1 hr⁻¹ to about 5^(hr−1) LHSV, or, in some examples, 0.5hr⁻¹ to 1.5 hr⁻¹. Additionally, a hydrogen treat gas rate of from about35.6 m³/m³ to about 1781 m³/m³ (200 SCF/B to 10,000 SCF/B) can be used.

Fractionation and Products

After hydro-processing, the hydro-processed oligomers in thehydro-processed stream 136 can be fractionated in the productdistillation column 138. Any number of fractions may be isolated,including, for example, a distillate stream 140 that may includehydrocarbon fluids, such as gasoline, naphtha, diesel, or a distillatefuel fraction, among others. Fractions that form base stocks forlubricants and other hydrocarbon products, may be isolated, including,for example, a light neutral stream 142, a medium neutral stream 144,and a heavy neutral stream 146. A bottoms stream 148 may also beisolated. In some examples, the bottoms stream 148 may be returned tothe hydro-processing reactor 132 for further processing.

FIG. 1(B) is a simplified block diagram of a separation system 108 forpurifying an impure ethylene stream formed from the dehydration ofethanol, in accordance with examples. Like numbered items are asdescribed with respect to FIG. 1. The separation system 108 may be assimple as a condenser 150. In this arrangement, the raw ethylene stream106, including ethylene, water from the initial azeotropic mixture, andwater from the dehydration process, is fed to the condenser 150. Acoolant-in stream 152 may include water from a cooling tower, or lowertemperature coolants for enhanced removal of water. A coolant-out stream154 may return the coolant, warmed by condensing water, to a coolantsystem. The condensed water may be removed in a water stream 156, whilethe ethylene in the oligomerization feed stream 110 exits through adifferent port on the vessel and is provided to downstream processingunits, such as the oligomerization reactor 112. As described herein,other water removal systems may be used, such as flash tanks, causticsystems, absorption systems, and the like. In some examples, thepurification system may remove other compounds, such as sulfur compoundsand nitrogen compounds, lowering poison concentrations before theoligomerization process.

FIG. 2 is a simplified block diagram of another system 200 for producingbase stocks from an ethanol feedstock, in accordance with examples. Likenumbered items are as described with respect to FIGS. 1(A) and 1(B). Theintermediate olefinic stream 122 is not limited to being upgraded bydimerization, but may be upgraded by other processes, such asalkylation.

As used herein, “alkylation” refers to a process in which a feed streamcontaining olefins, such the intermediate olefinic stream 122, isreacted with another stream containing hydrocarbons, such as a mixedxylene stream 158, among others, in an alkylation reactor 160. Theprocess converts at least a portion of the olefinic compounds to highermolecular compounds. The alkylation reactor 160 may react the feedstreams 122 and 158 in the presence of an acidic catalyst, such assulfuric acid or hydrofluoric acid, or a solid acid, such as a zeolite,for example zeolite Y, zeolite beta, and zeolite of the MWW family,among others. The alkylation may be run at a temperature of about 50° C.to about 300° C., and a pressure of about 150 psig to about 1000 psig.The process provides an alkylated stream 162 that may be processed insubsidiary units of the alkylation reactor 160 to remove acid and othercontaminants before being provided to a separation or distillationcolumn 164.

In the distillation column 164, light or unreacted compounds may beseparated into an unreacted stream 166 and blended with the intermediateolefinic stream 122 to be fed back into the alkylation reactor 160. Aheavy product stream 168 may be separated out and provided to theHDC/HDI reactor 132B.

FIG. 3 is a process flow diagram of a method 300 for producing basestocks from an ethanol feedstock, in accordance with examples. Themethod 300 begins at block 302, with the dehydration of an ethanolstream to form an impure ethylene mixture. As described herein, theimpure ethylene mixture may include ethylene, water, and low amounts ofother contaminants, depending on the purification process for theethanol stream.

At block 304, an ethylene stream may be recovered from the impureethylene mixture. This may be performed by passing the impure ethylenestream through a condenser to remove water from the impure ethylenestream. Other actions may be performed for the purification, including,for example, passing the output stream from the condenser through acoldbox to remove any remaining traces of water or other contaminants.

At block 306, the ethylene stream may be oligomerized to form a rawoligomer stream. As described herein, this may be performed bycontacting the ethylene stream with a homogeneous catalyst to form theraw oligomer stream, wherein the raw oligomer stream may have asubstantial concentration of linear alpha olefins.

At block 308, a light olefinic stream may be distilled from the rawoligomer stream. The light olefinic stream may include compounds havingbetween about four and about 12 carbons. At block 310 the light olefinicstream is blended with the ethylene stream prior to oligomerization. Asnoted herein, an olefinic stream may not include 100% olefiniccompounds, but may include other compounds, such as paraffiniccompounds, that have a similar boiling point to the olefinic compounds.

At block 312, a heavy olefinic stream is distilled from the intermediatestream. At block 314, the heavy olefinic stream is hydro-processed toform a hydro-processed stream. In the hydro-processing, the heavyolefinic stream may be hydrodemetallated to remove any traces ofcatalyst remaining from the oligomerization. The heavy olefinic streammay then be hydrocracked to form lower molecular weight compounds, forexample, having a broader distribution. The heavy olefinic stream may behydroisomerized to form a distribution of different isomers. Further,the heavy olefinic stream may be finished to decrease unsaturated andaromatic compounds in the hydro-processed stream.

At block 316, the hydro-processed stream is distilled to form the basestock. Distilling the hydro-processed stream may include separating adistillate stream, a naphtha stream, or both from the hydro-processedstream. Further, distilling the hydro-processed stream may includeforming a heavy neutral oil stock stream, a medium neutral oil stockstream, or a light neutral oil stock stream, or any combinationsthereof.

The method may include more or fewer steps than described with respectto FIG. 3. For example, an intermediate olefinic stream, includingcompounds having between about 12 and about 22 carbon atoms, may bedistilled from the raw oligomer stream and upgraded in molecular weight.As described with respect to FIGS. 1 and 2, this may be performed bydimerization or alkylation.

EXAMPLES Example 1: Linear Alpha Olefins of Different Schulz-FloryMolecular Distribution may be Produced from Ethylene using a HomogeneousCatalyst

The molecular distribution may be controlled by the catalyst, forexample, through the ligands. FIG. 4 is a drawing 400 of relatedhomogeneous catalysts, having different ligands, that may be used forthe oligomerization or dimerization processes, in accordance withexamples. The catalysts are labeled A-D, and are described further withrespect to the oligomerization reactions. Catalyst E may be used in thedimerization process.

The tests of the catalysts in the oligomerization process were performedin a 500 milliliter (mL) autoclave. A 100 mL toluene solution containing20 micromoles (μmol) catalyst and 4000 μmol MAO activator was charged tothe autoclave. Then a predetermined amount of N₂, or a mixture of H₂ andN₂ in some examples, as described with respect to Tables 1-3, wascharged into the autoclave to bring the autoclave to a preset pressure.The autoclave was then heated to 50° C. before ethylene was introduced.The reaction was exothermic and ethylene addition was controlled to keepthe temperature below about 120° C. and a final total pressure of about400 psi. The oligomerization reaction was allowed to proceed forapproximately 30 minutes.

The autoclave was then cooled to room temperature and overhead gaspressure was released via opening of a valve. The reaction product, inthe form of a solution or suspension was then recovered, quenched withan aqueous HCl solution, and the aqueous phase containing Fe and Al wasdiscarded. The reaction product was analyzed via gas chromatography (GC)and nuclear magnetic resonance (NMR) techniques.

The gas chromatography analysis for ethylene oligomers was performedusing method to enable coverage up to C30. The column was 30 m long,with an inner diameter of 0.32 millimeters and a packing of 0.25 μm,available as a HP-5 column from Agilent. The carrier gas was nitrogen.The injector was held at a temperature of 150° C. and 10 psi. A 50 to 1split ratio was used with a 121 mL per minute (mL/min) total flow rateand an injection size of 1-5 μL. The column oven was set to a 50° C.initial temp with a 10° C./min ramp rate to a 320° C. final temperature.It was held at the 320° C. temperature for 8 minutes giving a total runtime of 35 minutes. The detector was a flame ionization detector held at300° C., using a 30 mL/min flow of hydrogen, a 250 mL/min flow of air,and a 25 mL/min makeup stream of nitrogen. The gas chromatographyanalysis for dimerization or alkylation products was performed using ahigh temperature method to enable coverage up to C100. The column was 6m long, with an inner diameter of 0.53 millimeters and a packing of 0.15μm, available as a MXT-1 SimDist column from Restek company of StateCollege, Pa. The carrier gas was nitrogen. The injector was held at atemperature of 300° C. and 0.9 psi. A 15 to 1 split ratio was used witha 27.4 mL per minute (mL/min) total flow rate and an injection size of 1μL. The column oven was set to an 80° C. initial temp with a 15° C./minramp rate to a 400° C. final temperature. It was held at the 400° C.temperature for 15 minutes giving a total run time of 36.3 minutes. Thedetector was a flame ionization detector held at 300° C., using a 40mL/min flow of hydrogen, a 200 mL/min flow of air, and a 45 mL/minmakeup stream of nitrogen.

Another gas chromatography analysis was performed using a hightemperature method to enable coverage up to C100. The column was 6 mlong, with an inner diameter of 0.53 millimeters and a packing of 0.15μm, available as a MXT-1 SimDist column from Restek company of StateCollege, Pa. The carrier gas was nitrogen. The injector was held at atemperature of 300° C. and 0.9 psi. A 15 to 1 split ratio was used witha 27.4 mL per minute (mL/min). Total flow rate and an injection size of1 μL. The column oven was set to an 80° C. initial temp with a 15°C./min ramp rate to a 400° C. final temperature. It was held at the 400°C. temperature for 15 minutes giving a total run time of 36.3 minutes.The detector was a flame ionization detector held at 300° C., using a 40mL/min flow of hydrogen, a 200 mL/min flow of air, and a 45 mL/minmakeup stream of nitrogen.

The C-13 NMR analysis was performed using a Bruker 400 MHz Advance IIIspectrophotometer. The samples were dissolved in chloroform-D (CDCl₃) ortoluene-D8 in a 5 mm NMR tube at concentrations of between 10 to 15 wt.% prior to being inserted into the spectrophotometer. The C-13 NMR datawas collected at room temperature (20° C.). The spectra were acquiredwith time averaging to provide a signal to noise level adequate tomeasure the signals of interest. Prior to data analysis, spectra werereferenced by setting the chemical shift of the CDCl₃ solvent signal to77.0 ppm.

H-1 NMR data was collected at room temperature. The data was recordedusing a maximum pulse width of 45 degree, 8 seconds between pulses andsignal averaging of 120 transients.

The analyses confirmed that the products were mostly linearalpha-olefins (LAOs) having Schulz-Flory (S-F) distributions. The S-Fdistribution constant, u, was determined by an average of the molarratios of C16/C14; C14/C12; and C12/C10 in the product, as determined bygas chromatography.

The information in Table 1 shows the basic comparison betweenoligomerizations performed using catalysts A-D. For these runs, thereaction conditions included about 200 psi or ethylene, about 200 psi ofhydrogen, a reaction temperature of about 80° C. to 100° C., 100 mL oftoluene (as a catalyst solvent), 20 μmol of catalyst, and a ratio of 200mol/mol of activator (co-catalyst) to catalyst, such as the MAOactivators described herein.

TABLE 1 Comparison of oligomerization by catalyst A-D Alpha % Linear %Branched % Linear Example Catalyst Value Alpha Olefin* Olefins*Paraffin* X1 A 0.339 66.6 22.1 1.6 X2 B 0.667 92.9 5.2 1.2 X3 C 0.82896.0 1.1 2.4 X4 D 0.947 34.5 0.2 64.7 *Presented in C12 fraction asdetermined by gas chromatography and mass spectrometry

Catalyst B was chosen to determine the effects of changing the ratio ofhydrogen to nitrogen on the reaction. The results are shown in Table 2.For these runs, the reaction conditions included about 200 psi orethylene, about 200 psi of hydrogen or a mixture of hydrogen andnitrogen, a reaction temperature of about 80° C. to 100° C., 100 mL oftoluene, 20 μmol of catalyst, and a ratio of 200 mol/mol of activator(co-catalyst) to catalyst. As can be seen by the results in Table 2,changing the hydrogen to nitrogen ratio has relatively small effects onthe operation of the catalyst.

TABLE 2 comparison of oligomerization under changing ratios of hydrogenand nitrogen using catalyst B % Linear H2/N2, Alpha Alpha % Branched %Linear Example Catalyst psi Value Olefin* Olefins* Paraffin* X2 B200/0   0.667 92.9 5.2 1.2 X5 B 20/180 0.666 92.2 6.3 0.8 X6 B  2/1980.698 89.2 8.6 1.1 *Presented in C12 fraction as determined by gaschromatography and mass spectrometry

Catalyst C was chosen to determine the effects of changing the solventfor the reaction. The results are shown in Table 3. For these runs, thereaction conditions included about 200 psi or ethylene, about 200 psi ofhydrogen or a mixture of hydrogen and nitrogen, a reaction temperatureof about 80 to 100° C., 100 mL of a solvent as identified in Table 3,20-40 μmol of catalyst, and a ratio of 100-200 mol/mol of activator(co-catalyst) to catalyst.

TABLE 3 comparison of oligomerization using different solvents andcatalyst C % Linear Alpha Alpha % Branched % Linear Example CatalystSolvent Value Olefin* Olefins* Paraffin* X3 C Toluene 0.828 96.0 1.1 2.4X7 C Isohexane 0.825 92.2 1.28 3.7 X8 C Cyclohexane 0.826 91.4 1.87 3.9*Presented in C12 fraction as determined by gas chromatography and massspectrometry

The results of the runs in Tables 1-3 indicate that controlling theligands of the catalyst may be used to control both the paraffin/olefinratio and the S-F distribution product composition. It may also be notedthat the oligomerization using catalysts A-D is tolerant of a largeamount of H₂ and a variety of solvents.

FIG. 5 is a plot 500 of the Schultz-Flory distribution of a product thatincludes different carbon numbers, in accordance with examples. Theweight fraction of the Schulz-Flory product distribution withexperimentally obtained a values may be plotted against the carbonnumber in the product. The same data can be recast to show lumpedfraction distribution as a function of a value.

FIG. 6 is a plot 600 of the effect of the change in carbon numbercomposition on a weight fraction of a product as the Schultz-Florydistribution changes, in accordance with examples. The plot 600 showsC24−, C24-C50, and C52+ fractions as a function of a value, indicatingthat the lube molecule range C24-C50 has a maximum value of about 40 wt.% at an a value around 0.88. This further illustrates that the lube/LAOsplit may be effectively controlled by using different catalysts thatoffer different a values.

Example 2: Dimerizing an Intermediate Olefinic Stream (C14-C24) intoLube Range Molecules

The dimerization may be performed by either heterogeneous catalysts,such as solid acid catalysts, or homogeneous organometallic catalysts.For example, solid acids include proton form zeolite, acid treated clay,amorphous silica-alumina, acid form ion-exchange resins, and variousWO₃/ZrO₂ mixed metal oxides.

To test the dimerization, a 19-g mixture of C14-C24 linear alpha olefinswas treated with 200 mg of Catalyst E and 1 mL of MAO (30% Al) at roomtemperature overnight. The resulting mixture was diluted with hexane andthen hydrolyzed with aqueous HCl.

FIGS. 7(A) and 7(B) are plots of gas chromatograms illustrating thechanges caused by dimerization 702 of the alpha olefin mixture, inaccordance with examples. The plots 700 are of the starting material 704and the product 706. The plot of the starting material 704 shows a firstset of peaks 708 from the C14-C24 linear alpha-olefins (LAOs) generatedby a homogeneous catalyst, such as catalyst E.

After dimerization, a second set of peaks 710 show a significantdecrease in the amount of C14-C24 LAOs, as well as some broadening,indicating reaction of the LAOs. A new set of peaks 712 is present afterthe reaction, corresponding to C26 to C52 (and higher) olefins. Thisillustrates the effectiveness of dimerization in increasing themolecular weight of the LAOs. Other techniques, such as alkylation, maybe used to increase the molecular weight of the LAOs.

Example 3: Hydroisomerizing Lube Range Olefin Molecules to Lube Oil

The hydroisomerization of olefins may broaden the molecular weightdistributions of the olefins, improving characteristics such as pourpoint, VI, and others. This may be performed by a number of acidcatalysts, such as the ZSM-48 catalyst described in the synthesisprocedure below.

Preparation of Formulated ZSM-48 Catalyst

To form a bound ZSM-48 catalyst, 65 parts ZSM-48 zeolite crystals arecombined with 35 parts pseudoboehmite alumina dry powder, on a calcineddry weight basis. The ZSM-48 and the pseudoboehmite alumina dry powderare placed in a muller or a mixer and mixed for about 10 to 30 minutes.Sufficient water is added to the ZSM-48 and alumina during the mixingprocess to produce an extrudable paste.

The extrudable paste is formed into a 1/16 inch quadralobe extrudateusing an extruder. After extrusion, the 1/16th inch quadralobe extrudateis dried at a temperature ranging from about 250° F. (about 120° C.) toabout 325° F. (about 163° C.). After drying, the dried extrudate isheated to about 1000° F. (about 538° C.) under flowing nitrogen. Theextrudate is then cooled to ambient temperature and humidified withsaturated air or steam. After the humidification, the extrudate is ionexchanged with about 0.5 to about 1 N ammonium nitrate solution. Theammonium nitrate solution ion exchange is repeated. The ammonium nitrateexchanged extrudate is then washed with deionized water to removeresidual nitrate prior to calcination in air. After washing the wetextrudate, it is dried. The exchanged and dried extrudate is thencalcined in a nitrogen/air mixture to about 1000° F. (about 538° C.).Following calcination, the extrudate was exposed to steam at about 700°F. (about 371° C.) for about three hours.

The formulated ZSM-48 catalyst was added to the dimerized productdescribed with respect to FIG. 7(A) in Example 2. The mixture was heatedin an closed autoclave at hydroisomerization condition of about 200-250°C. and about 500-1000 psi H₂ for 1 to 5 days.

FIGS. 8(A) and 8(B) are plots of gas chromatograms illustrating thechanges caused by hydroisomerization 802 of an olefin mixture 804, inaccordance with examples. As shown in FIG. 8(A), and described withrespect to FIG. 7(A), the olefin mixture 804 includes C14-C24 olefins806 and C28-C52 olefins 808. The gas chromatogram of the reactionproducts 810, including isomerized C14-C24 812 and isomerized C28-C52814, is shown in FIG. 8(B). GC traces of the before and afterhydroisomerization materials are shown below, which clearly indicateisomerization of the molecules (broadening of peaks).

FIG. 9 is a plot 900 of the DEPT-135 C-13 NMR spectra illustrating thechanges caused by hydroisomerization 902 of an alpha olefin mixture, inaccordance with examples. As used herein, DEPT is an acronym fordistortionless enhancement by polarization transfer. The technique isused to determine the multiplicity of carbon atoms substitution withhydrogen. The DEPT-135 C-13 NMR spectra of the products ofhydroisomerization of dimerized C14-C24 LAOs show the presence ofisolated methyl (CH3, ˜20 ppm) branching 904, and the associated methine(CH, ˜32 ppm) carbon 906 and methylene carbons 908 (CH2, ˜27 and ˜37ppm) adjacent to the methine (CH) carbon.

TABLE 4 Comparisons of dimerized and hydroisomerized products. ExampleX9 X10 X11 X12 Description Dimerized Hydro- Dimerized Hydro- C14-C24isomerized C14 + isomerized LAO X9 LAO X11 Mn by GPC 412 374 464 405 Mwby GPC 466 437 658 463 PD by GPC 1.13 1.17 1.42 1.14 Tm by DSC, ° C.25.4 6.4 47.0 30.2 Tg by DSC, ° C. −16.5 −66.5 −5.4 −25.2

In Table 4, Mn is the number averaged molecular weight, Mw is the weightaveraged molecular weight, and PD is the polydispersity, calculated asMw/Mn. The GPC or gel permeation chromatography is calibrated withpolyethylene standards. DSC is differential scanning calorimetry. Tm isthe melting point or crystallization temperature of the material and Tgis the glass transition temperature of the material.

Example 4: LAO Recycle and Reactions with Ethylene in theOligomerization Reaction Zone

It is also anticipated that the non-lube range LAO can be incorporatedinto the ethylene oligomers during the oligomerization process. Theresults of the tests are shown in Table 5. For these runs, the reactionconditions included about 100 or 200 psi or ethylene, about 200 psi ofhydrogen, a reaction temperature of about 80 to 100° C., 100 mL oftoluene, 20 μmol of catalyst C or E, and a ratio of 100-200 mol/mol ofactivator (MAO co-catalyst) to catalyst.

This is demonstrated by addition of 1-pentene after introduction ofethylene to the system. The incorporation of 1-pentene is evident in theresults shown in Table 5 by the increasing amount of odd number olefinssuch as tridecenes (C13 olefins) as well as branched isomers within theodd number olefins, which indicates the incorporation of an alreadyformed LAO into a growing LAO chain, causing branching. For Table 5, theS-F distribution constant, a, was determined by averaging the molarratios: C16/C14; C14/C12; and C12/C10 in the product, as determined bygas chromatography, as described herein.

TABLE 5 Incorporation of 1-pentene into oligomers. C12 Fraction C13Fraction % Linear % Linear 1-Pentene C2H4/H2, Alpha % in Alpha %Branched % in Alpha % Branched Example Catalyst added psi ValueC10-C20** Olefin* Olefins* C10-C20** Olefin* Olefins* X3 C No 200/2000.828 17.5 96.0 1.1 0.5 78.9 13.8 X13 C Yes 200/200 0.845 16.4 92.3 1.21.6 64.3 26.4 X14 C Yes 100/200 0.869 14.2 87.0 1.8 3.4 49.0 39.4 X15 ENo 200/200 0.678 21.7 92.9 4.2 0.5 70.8 20.7 X16 E Yes 200/200 0.74117.9 87.1 8.5 2.9 51.2 39.3 *Presented in C12 or C13 fractions asdetermined by gas chromatography and mass spectrometry **Normalized toC10-C20

EMBODIMENTS

The embodiments of the present techniques include any combinations ofthe examples in the following numbered paragraphs.

1. A system for manufacturing a base stock from an ethanol stream,including a dehydration reactor configured to form an impure ethylenestream from the ethanol stream, a recovery system configured to purifythe impure ethylene stream to form an ethylene stream, and anoligomerization reactor configured to oligomerize the ethylene stream toform a raw oligomer stream. The system also includes a distillationcolumn configured to separate the raw oligomer stream into a lightolefinic stream, an intermediate olefinic stream, and a heavy olefinicstream, wherein the light olefinic stream is blended with the ethylenestream to form a blended stream, and the blended stream is provided tothe oligomerization reactor. A hydro-processing system is configured tohydroprocess the heavy olefinic stream to form a hydroprocessed stream,and a product distillation column is configured to separate thehydroprocessed stream to form the base stock.

2. The system of embodiment 1, including a dimerization reactorconfigured to dimerize the intermediate olefinic stream and return adimerized stream to the distillation column.

3. The system of either embodiments 1 or 2, including an alkylationreactor configured to alkylate the intermediate olefinic stream andprovide an alkylated stream to an alkylation distillation column.

4. The system of embodiment 3, wherein the alkylation distillationcolumn is configured to separate an unreacted olefin stream from thealkylated stream and return the unreacted olefin stream to thealkylation reactor.

5. The system of any of embodiments 1 to 4, including a bioreactor togenerate the ethanol stream.

6. The system of any of embodiments 1 to 5, wherein the dehydrationreactor includes a fluidized bed reactor including a heterogeneouscatalyst.

7. The system of any of embodiments 1 to 6, wherein the oligomerizationreactor is configured to use a homogeneous catalyst.

8. The system of embodiment 7, wherein the homogeneous catalyst includesan iron (II) pyridine-bis-imine (Fe—PBI) catalyst including a structureof

wherein Rn includes one, two, or three substituents, and wherein thesubstituents include CH₃, F, or both.

9. The system of any of embodiments 1 to 8, wherein the hydro-processingsystem includes a demetallation unit.

10. The system of any of embodiments 1 to 9, wherein thehydro-processing system includes a hydrocracking unit.

11. The system of any of embodiments 1 to 10, wherein thehydro-processing system includes a hydroisomerization unit.

12. The system of any of embodiments 1 to 11, wherein the productdistillation column is configured to separate the hydroprocessed streaminto a distillate stream including naphtha, a heavy neutral stream, amedium neutral stream, and a light neutral stream.

13. A method for manufacturing a base stock from an ethanol stream,including dehydrating an ethanol stream to form an impure ethylenestream, recovering an ethylene stream from the impure ethylene stream,and oligomerizing the ethylene stream to form a raw oligomer stream. Themethod also includes distilling a light olefinic stream from the rawoligomer stream and blending the light olefinic stream into the ethylenestream prior to the oligomerization. A heavy olefinic stream isdistilled from the raw oligomer stream, and the heavy olefinic stream ishydro-processed to form a hydroprocessed stream. The hydroprocessedstream is distilled to form the base stock.

14. The method of embodiment 13, wherein dehydrating the ethanol streamincludes reacting the ethanol stream over an acid catalyst to formethylene and water.

15. The method of either embodiments 13 or 14, wherein dehydrating theethanol stream includes reacting the ethanol stream over a zeolitecatalyst to form ethylene and water.

16. The method of any of embodiments 13 to 15, including distilling anintermediate olefinic stream from the raw oligomer stream.

17. The method of embodiment 16, including dimerizing the intermediateolefinic stream to form a dimerized stream, and distilling the dimerizedstream with the raw oligomer stream.

18. The method of embodiment 16, including alkylating the intermediateolefinic stream to form an alkylated stream, distilling the alkylatedstream to form a lights stream and a heavies stream, combining thelights stream with the intermediate olefinic stream to form a combinedstream, and alkylating the combined stream.

19. The method of embodiment 18, including hydro-processing the heaviesstream.

20. The method of embodiments 13 to 19, wherein oligomerizing theethylene stream includes contacting the ethylene stream with ahomogeneous catalyst including an iron (II) pyridine-bis-imine.

21. The method of embodiments 13 to 20, including separating anunreacted ethylene stream from the raw oligomer stream, andoligomerizing the unreacted ethylene stream with the ethylene stream.

22. The method of embodiments 13 to 21, including distilling a lightlinear alpha olefin stream from the raw oligomer stream.

23. The method of embodiments 13 to 22, distilling a heavy linear alphaolefin stream from the raw oligomer stream.

24. The method of embodiments 13 to 23, wherein hydro-processing theheavy olefinic stream includes hydrocracking the heavy olefinic stream.

25. The method of embodiments 13 to 24, wherein hydro-processing theheavy olefinic stream includes hydroisomerizing the heavy olefinicstream.

26. The method of embodiments 13 to 25, wherein distilling thehydroprocessed stream includes separating a distillate stream, a naphthastream, or both from the hydroprocessed stream.

27. The method of embodiments 13 to 26, wherein distilling thehydroprocessed stream includes forming a heavy neutral oil stock stream,a medium neutral oil stock stream, or a light neutral oil stock stream,or any combinations thereof.

28. A system for manufacturing a base oil stock from ethanol, includinga dehydration reactor to form an impure ethylene stream from an ethanolstream, a recovery system to form an ethylene stream from the impureethylene stream, and an oligomerization reactor configured to convertthe ethylene stream to a raw olefinic stream by contacting the ethylenestream with a homogeneous catalyst. The system includes a distillationcolumn configured to separate a light olefinic stream and a heavyolefinic stream from the raw olefinic stream and to combine the lightolefinic stream into the ethylene stream to the oligomerization reactor.A hydro-processing reactor is configured to hydroprocess the heavyolefinic stream to form a hydroprocessed stream, and a productdistillation column to separate the hydroprocessed stream to form anumber of base stock streams.

29. The system of embodiment 28, wherein the distillation column isconfigured to separate an intermediate olefinic stream from the rawolefinic stream.

30. The system of embodiment 29, including a dimerization reactorconfigured to dimerize the intermediate olefinic stream to form adimerized stream and return the dimerized stream to the distillationcolumn.

31. The system of embodiment 29, including an alkylation reactorconfigured to alkylate the intermediate olefinic stream to form analkylated stream.

32. The system of embodiment 31, including an alkylation distillationcolumn configured to separate the alkylated stream into a reacted streamand an unreacted stream, and return the unreacted stream to thealkylation reactor.

33. The system of any of embodiments 28 to 32, wherein the homogeneouscatalyst includes an iron (II) pyridine-bis-imine (Fe—PBI) compoundincluding a structure of

wherein Rn includes one, two, or three substituents, and wherein thesubstituents include CH₃, F, or both.

34. The system of any of embodiments 28 to 33, wherein thehydroprocessed stream is demetallated, hydrocracked, or hydroisomerized,or any combination thereof.

While the present techniques may be susceptible to various modificationsand alternative forms, the examples discussed above have been shown onlyby way of example. However, it should again be understood that thetechniques is not intended to be limited to the particular examplesdisclosed herein. Indeed, the present techniques include allalternatives, modifications, and equivalents falling within the truespirit and scope of the appended claims.

The invention claimed is:
 1. A method for manufacturing a base stockfrom an ethanol stream, comprising: dehydrating an ethanol stream toform an impure ethylene stream; recovering an ethylene stream from theimpure ethylene stream; oligomerizing the ethylene stream to form a rawoligomer stream; distilling a light olefinic stream, an intermediateolefinic stream and a heavy olefinic stream from the raw oligomer streamand recycling the light olefinic stream to the ethylene stream;alkylating the intermediate olefinic stream to form an alkylated stream;distilling the alkylated stream to form a lights stream and a heaviesstream; recycling the lights stream to the intermediate olefinic stream;subjecting the heavy olefinic stream to hydrodemetallation to form afirst hydroprocessed stream; subjecting the first hydroprocessed streamand the heavies stream to hydrocracking and/or hydroisomerization toform a second hydroprocessed stream; and distilling the secondhydroprocessed stream to form the base stock.
 2. The method of claim 1,wherein said dehydrating the ethanol stream comprises reacting theethanol stream over an acid catalyst to form ethylene and water.
 3. Themethod of claim 1, wherein said dehydrating the ethanol stream comprisesreacting the ethanol stream over a zeolite catalyst to form ethylene andwater.
 4. The method of claim 1, wherein oligomerizing the ethylenestream comprises contacting the ethylene stream with a homogeneouscatalyst comprising an iron (II) pyridine-bis-imine.
 5. The method ofclaim 1, comprising: separating an unreacted ethylene stream from theraw oligomer stream; and recycling the unreacted ethylene stream to theethylene stream.
 6. The method of claim 1, wherein the light olefinicstream comprises light linear alpha olefins.
 7. The method of claim 1,wherein the heavy olefinic stream comprises heavy linear alpha olefins.8. The method of claim 1, wherein said distilling the secondhydroprocessed stream comprises separating a distillate stream, anaphtha stream, or both from the second hydroprocessed stream.
 9. Themethod of claim 1, wherein said distilling the second hydroprocessedstream comprises forming a heavy neutral oil stock stream, a mediumneutral oil stock stream, or a light neutral oil stock stream, or anycombinations thereof.